A complete alternative and cheaper route for production of glassy polymeric carbon electrodes in laboratorial scale is described. Two kinds of polyphenolic resins were synthesized by mixing the precursors phenol and formaldehyde with 1) ammonium or 2) sodium hydroxide as catalyst. A shorter treatment time of 3.5 days (from 25 to 1000 °C) was employed for preparation of the electrodic material compared with the 5–7 day period proposed in the literature. The obtained materials were inserted into conventional hollow plastic bodies and electrically contacted with copper wire. After proper polishing, the electrodic materials were tested as working electrodes by cyclic voltammetry technique. The data demonstrated that the use of sodium hydroxide causes peculiar problems such as alkaline residues in the electrodic materials and subsequent fading of final product. On the other hand, the materials obtained by the ammonium hydroxide route presented good results in terms of mechanical resistance, glassy appearance, conductivity and voltammetric response, allowing for application of such materials in electrochemistry.